JP4395443B2 - Potassium ionomers modified with organic acid salts and structures made therefrom - Google Patents

Description

  The present invention relates to an antistatic polymer composition. More specifically, it relates to an antistatic ethylene acid copolymer ionomer composition.

(Cross-reference of related applications)
This application claims priority from US Provisional Patent Application No. 60 / 427,782, filed Nov. 20, 2002.

  In general, manufactured articles made from polymeric materials can be electrostatically charged and their surfaces can attract and retain charged particles such as dust in the air. In some cases, the article can be damaged and / or otherwise diminished by the deposition of electrostatically charged species. In order to prevent the adhesion of charged particles, various approaches for preventing surface static charge accumulation have been proposed and put into practical use.

  Antistatic agents can be incorporated into the composition of the molded article, or antistatic agents can be applied to the surface of the article as a way to prevent static charge buildup on the article. The use of antistatic agents is not without trouble. The material in contact with the composition can become soiled due to bleeding of the antistatic agent from the composition, and / or the antistatic effect can diminish over time. Antistatic agents can be ineffective when applied to ionomers. The deposited antistatic film can have insufficient mechanical properties and can be easily damaged, have unsatisfactory water resistance, or become tacky due to water absorption.

A subsurface antistatic polymer layer can be used to avoid problems encountered by exposing the antistatic layer to the surface of the article. In Patent Document 1, an ionic conductive resin layer is formed on a plastic film, and a water-resistant plastic layer having a volume resistance of 1 × 10 ¹³ Ω · cm or less and a thickness of 10 μm or less is ionic conductive. An antistatic plastic film formed on the surface of resin positive is disclosed.

  (Patent Document 2) discloses an antifouling laminate having an alkali metal salt or an amine salt of an ethylene-unsaturated carboxylic acid copolymer as an intermediate layer. (Patent Document 3) discloses a dust-proof laminate having a composition containing a thermoplastic resin composed of a potassium ionomer of ethylene-unsaturated carboxylic acid and a polyhydroxy compound as an intermediate layer.

JP-B-2-28919 JP 61-44646 A Japanese Patent Laid-Open No. 10-193495 US Pat. No. 5,198,401 US Pat. No. 5,405,922

In one aspect, the present invention provides:
(1) (i) E is ethylene, X is _C 3 -C ₈ alpha, a β-ethylenically unsaturated carboxylic acid, Y is an alkyl acrylate and alkyl groups having 1 to 8 carbon atoms At least one E / X / Y copolymer that is a softening comonomer selected from alkyl methacrylates, wherein X is about 2-30% by weight of the E / X / Y copolymer, and Y is E / An E / X / Y copolymer that is about 0-40% by weight of the X / Y copolymer;
(Ii) at least one polymer layer comprising a blend with one or more organic acids or salts thereof wherein the combined acid carboxylate functionality of the blend is at least partially neutralized by potassium; 2) A multilayer article comprising at least one surface layer.

  In one embodiment, the present invention is an article comprising an acid copolymer ionomer blend having antistatic properties. Acid copolymer ionomers (“ionomers”) are ions formed from olefins such as ethylene, carboxylate salts of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, or maleic acid, and optionally softening comonomers. It is a copolymer. As used herein, the term “copolymer” can describe a polymer obtained by copolymerization of at least two different monomer species. The term “terpolymer” is used to specifically describe a copolymer resulting from the copolymerization of three different monomer species. At least one alkali metal, transition metal, or alkaline earth metal cation, such as lithium, sodium, potassium, magnesium, calcium, or zinc, or a counterion where a combination of such cations neutralizes the carboxylate anion of the salt possible. Particularly preferred are ionomers that are at least partially neutralized with potassium cations. Ternary copolymers can also be made from softened comonomers such as olefins such as ethylene, unsaturated carboxylic acids and alkyl (meth) acrylates that provide “softer” resins, and are more neutralized. Soft ionomers can be formed.

The blends of the present invention are: (i) an acrylic wherein E is ethylene, X is a C ₃ -C ₈ α, β ethylenically unsaturated carboxylic acid, and Y is an alkyl group having 1 to 8 carbon atoms At least one E / X / Y copolymer that is a softening comonomer selected from alkyl acrylates and alkyl methacrylates, wherein X is about 2-30% by weight of the E / X / Y copolymer; Includes an ionomer comprising an E / X / Y copolymer that may be present in an amount of from about 0 to about 40% by weight of the E / X / Y copolymer. Suitable ionomers for use in the practice of the present invention are known and are commercially available from the assignee of the present application under the trade name Surlyn®.

  In addition, the blends of the present invention include a second component that is a salt of an organic acid. The blends of the present invention can comprise at least about 5% by weight organic salts. Preferably, the blend contains no more than about 50% by weight. More preferably the blend comprises at least about 10% by weight organic acid or salt, even more preferably at least about 20% by weight and most preferably at least about 30% by weight organic acid or salt thereof. The organic salt is preferably at least partially neutralized with potassium ions. Preferably, more than 80% of all the acid components in the blend are neutralized, more preferably more than 90%. Most preferably, 100% of all the acid components in the blend are neutralized. The organic acid used in the present invention is particularly non-volatile and non-migratory. Non-limiting exemplary examples of organic acids are stearic acid, oleic acid, erucic acid and behenic acid. Stearic acid and oleic acid and their ionomers are preferred. Even more preferred are branched isomers of suitable organic acids, such as branched isomers of stearic acid and oleic acid, such as, for example, isostearic acid and isooleic acid. A more complete description of acids and blends suitable for use in the present invention was filed on Nov. 11, 2003, “Moisture and Gas Permeable Non-Porous Ionomer Films”. US patent application entitled “Films)”.

  Optionally, the antistatic composition of the present invention can comprise a polymer that can be blended into the composition. However, if the inclusion of other optional components adversely affects the antistatic properties of the articles of the present invention, or for any other reason, some thermoplastic polymers or the optional components may be excluded. it can. The compositions described herein can have other desirable properties that can be negatively affected by blending the antistatic composition with other polymer components. For example, the moisture and gas permeability of the sheet film can be negatively affected by such blends.

  Optional polymer components that can be blended with the antistatic compositions of the present invention include conventional ionomer copolymers, i.e., antistatic properties, including binary polymer ionomers and terpolymer ionomers. Not ionomers, as well as non-ionic thermoplastics. Non-ionic thermoplastic resins include, but are not limited to, illustrative examples and are intended to be polyurethanes, poly-ether-esters, poly-amide-ethers, polyether-ureas, PEBAX (Atochem) A commercially available group of block copolymers based on polyether-block-amide); styrene-butadiene-styrene (SBS) block copolymers; styrene (ethylene-butylene) -styrene block copolymers Polyamide (oligomer and polymer); Polyester; Polyvinyl alcohol; Polyethylene, including polyethylene, polypropylene, ethylene / propylene copolymer; Ethylene and vinyl acetate, (meth) acrylate, (meth) acrylic acid, epoxy functionality Mono -Copolymers with various comonomers such as CO, vinyl alcohol; polymers functionalized by maleic anhydride grafting, epoxidation; EPDM, metallocene catalyzed PE and copolymers, thermoset elastomers Thermoplastic elastomers such as powdered elastomers are included.

  When included, the amount of optional polymer component is preferably no greater than 95%, more preferably no greater than 90%, and particularly preferably no greater than 60% by weight of the total potassium ionomer composition. In other words, the potassium ionomer preferably accounts for 5% by weight or more of the total composition, more preferably 10% by weight or more, and particularly preferably 40% by weight or more.

  It may be preferable to incorporate a thermoplastic polymer selected from polymeric materials that can be used in the surface of the laminate, such as those described below. Among these materials, olefin-based polymers, particularly ethylene homopolymers, copolymers of ethylene and α-olefins having 3 or more carbon atoms, and ethylene and vinyl acetate and unsaturated carboxylic acid esters. The use of ethylene-based polymers selected from copolymers with such unsaturated esters is preferred. There is no need to use new materials such as ethylene-based polymers. For example, when ethylene-based polymers are used for the surface layer, non-standard products or molding waste such as ears formed during molding may be recycled.

  In the antistatic composition of the present invention, polyhydroxy compounds having two or more alcoholic hydroxyl groups can also be blended to improve antistatic properties. Specific examples of such compounds include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, polyoxyethylene-polyoxypropylene glycol of various molecular weights; polyhydric alcohols such as glycerin, hexanetriol, pentaerythritol and sorbitol and These ethylene oxide adducts include adducts of polyvalent amines and alkylene oxides. The effective blend ratio of the polyhydroxy compound is 15 wt% or less, preferably 10 wt% or less, more preferably 5 wt% or less, most preferably 0.1 wt%, based on the amount of the organic acid salt-modified potassium ionomer. % Or less.

  The compositions of the present invention can be used in single or multilayer structures to provide their antistatic properties. The compositions of the present invention may be useful in packaging applications such as films, containers, and lids.

  The antistatic composition of the present invention may be useful as an intermediate layer of a multilayer laminate. The composition constitutes the intermediate layer, the inner or “hidden” layer of the multilayer stack. The antistatic laminate of the present invention comprises a layer structure comprising at least two layers, preferably three layers, comprising at least one surface layer and an intermediate layer, wherein the intermediate layer comprises the antistatic composition described above. It is a laminated body containing.

In yet another embodiment, the laminate of the present invention is a surface layer comprising a polymer material having a surface resistance of 1 × 10 ¹⁴ Ω or more, at least one of which is 10% attenuation of 20 seconds or less at an applied voltage of + 5000V. A surface layer having a time (10% decay time is measured at 23 ° C. in an atmosphere of 50% or 60% relative humidity) can be included.

A polymer material having a surface resistance of 1 × 10 ¹⁴ Ω or higher can be used for the surface layer (measured at 23 ° C. in an atmosphere of 50% relative humidity). This polymeric material is such that a molded article made solely of that material exhibits a surface resistance of 1 × 10 ¹⁴ Ω or higher. Specific examples thereof include ethylene homopolymers; copolymers of ethylene and α-olefins having 3 to 12 carbon atoms, such as high pressure polyethylene, medium or high density polyethylene, linear low density polyethylene, especially Linear low density polyethylene having a density of 940 kg / m ³ or less and very low density polyethylene; polypropylene; poly-1-butene; poly-4-methyl-1-pentene; copolymer of ethylene and a polar monomer; For example, an ethylene-vinyl acetate copolymer, a copolymer of ethylene and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, monoethyl maleate, maleic anhydride, or the like, Na, Li, K, Zn, Ionomers such as Mg, Ca; ethylene and at least one unsaturated carboxylic acid ester, for example Copolymers of methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, glycidyl methacrylate, dimethyl maleate; as described above with ethylene A copolymer of an unsaturated carboxylic acid and an unsaturated carboxylic acid ester, or an ionomer containing a cation selected from the group consisting of Na, Li, K, Zn, Mg, Ca, etc .; ethylene, carbon monoxide and A copolymer of an unsaturated carboxylic acid ester or vinyl acetate; an olefin-based polymer such as a polyolefin elastomer; a styrene-based polymer such as a rubber-reinforced styrene-based resin such as polystyrene, high-impact polystyrene, ABS resin, etc .; Polyesters such as terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, cyclohexanedimethanol-copolymerized polyethylene terephthalate, and polyester elastomer; polycarbonate; polymethyl methacrylate; or a mixture of two or more thereof Can be mentioned.

  Of such polymeric materials, the use of polymeric materials selected from zinc ionomers and ethylene-based polymers made with metallocene catalysts is preferred. This is because a laminate having excellent antifouling properties can be easily obtained without using any polyhydroxy compound in the intermediate layer.

  Zinc ionomers are obtained by partially neutralizing an ethylene-unsaturated carboxylic acid copolymer that may optionally be copolymerized with another polar monomer with zinc. Those in which other metal ions are present are also suitable.

  Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, monomethyl maleate, monoethyl maleate. Acrylic acid and / or methacrylic acid are particularly preferred. Examples of polar monomers that can serve as copolymerization components include vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic Unsaturated carboxylic acid esters such as acid n-hexyl, isooctyl acrylate, methyl methacrylate, dimethyl maleate and diethyl maleate; carbon monoxide. In particular, unsaturated carboxylic acid esters are suitable copolymerization components.

  The ethylene-unsaturated carboxylic acid copolymer as the base polymer of the zinc ionomer is preferably one having an unsaturated carboxylic acid content of about 1 to about 25% by weight, particularly about 5 to about 20% by weight. The content of the polar monomer that can be copolymerized is, for example, about 40% by weight or less, preferably about 30% by weight or less. Zinc ionomers having a degree of neutralization of about 10 to about 90%, particularly about 15 to about 80% are preferred. When workability and actual physical properties are considered, the melt index is about 0.1 to about 100 g / 10 min, preferably about 0.2 to about 50 g / 10 min, measured at 190 ° C. and 2160 g load. The use of ionomers having the following is preferred.

  Suitable ethylene-based polymers as polymer materials that can be used as the surface layer are ethylene homopolymers produced in the presence of a metallocene catalyst or ethylene and 3 or more (preferably 3 to 12) carbon atoms. (See, for example, US Patent Publication (Patent Document 4) and US Patent Publication (Patent Document 5)).

  Examples of α-olefins having 3 or more carbon atoms in the ethylene copolymer described above include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene and the like can be mentioned. In particular, a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms is preferably used. In some cases, two or more α-olefins may be present in a mixture that can be copolymerized with ethylene.

Various densities may be used depending on the alpha-olefin content in the copolymer, such as ethylene polymers or copolymers made in the presence of a metallocene catalyst. However, it is generally preferred to use an ethylene copolymer having a density of about 870 to about 970 kg / m ³ , especially about 890 to about 950 kg / m ³ , especially about 900 to about 940 kg / m ³ . When workability and actual physical properties are considered, the melt index is about 0.1 to about 100 g / 10 min, preferably about 0.2 to about 50 g / 10 min, measured at 190 ° C. and 2160 g load. The use of ionomers having the following is preferred.

  The laminate of the present invention can have at least two layers. Structures in which another polymeric material layer or adhesive layer is formed between at least one of the surface layers and the intermediate layer are contemplated herein. Such a polymer material layer may be a layer made of the polymer material mentioned as the surface layer, but it is preferably used in the collection of waste products such as ears formed during the manufacture of substandard products or laminates. It is a recovery layer. The material of such a recovery layer can be the same as the material of the surface layer, the intermediate layer or a mixture of these materials.

  The adhesive layer that can be formed between the surface layer and the intermediate layer can be any that can improve the adhesion between the surface layer and the intermediate layer. It can be selected from thermoplastic polymers such as those listed as examples of surface material, and can also be a hot melt adhesive or a coating type adhesive. It is preferable to use an adhesive that can be extrusion coated or coextruded selected from thermoplastic polymers and compositions including such thermoplastic polymers and tackifiers incorporated therein.

  When the polymers do not adhere well to each other, an anhydride or acid-modified ethylene and propylene homopolymer and copolymer can be extruded to improve bonding of the polymer layers together (also as a “tie” layer). Also improve layer-layer adhesion in multilayer structures. The composition of the tie layer will be determined by the composition of the adjacent layers that need to be joined in a multilayer structure. Those skilled in the polymer art can select an appropriate tie layer based on the other materials used in the structure. Various tie layer compositions are commercially available from the present applicant under the trade name Bynel®.

  Another preferred embodiment of the invention is that the first and second surface layers are made of low, medium or high density polyethylene or an ethylene-unsaturated ester copolymer such as an ethylene-vinyl acetate copolymer, A layered structure including a three-layer structure of a first surface layer (outer layer) / intermediate layer / second surface layer (inner layer), the layer of which is made of the organic acid-modified potassium ionomer composition of the present invention.

  The laminate of the present invention can be produced by laminating individual layers, preferably by extrusion coating, coextrusion or blow molding. The thickness of the total laminate is optional and depends on the application, but it is preferably, for example, from about 10 to about 3000 μm, especially from about 20 to about 1000 μm. In another embodiment of the present invention, at least one surface layer has a 10% decay time of 20 seconds or less, preferably 10 seconds or less, more preferably 1 second or less (necessary for the potential to decay from an applied voltage of + 5000V to + 500V. And 10% decay time measured at 23 ° C. in an atmosphere of 50% relative humidity. For this purpose, the intermediate layer is preferably not less than 5 μm, in terms of the thickness of the surface layer, or if a recovery layer or adhesive layer is formed, in terms of the total thickness of the surface layer and the additional layer. Preferably has a thickness of 10 μm or more, and the thickness of the surface layer of the attenuation characteristic shown above is preferably 500 μm or less, particularly preferably 300 μm or less. Furthermore, when practical performance is considered, the ratio of the thickness of the surface layer to the thickness of the intermediate layer (or when the recovery layer or adhesive layer is formed), the ratio of the total thickness of the surface layer and the additional layer is preferably about 0.1 to about 100 μm, more preferably about 0.5 to about 50 μm.

  Individual layers can incorporate various additives as needed, examples include antioxidants, light stabilizers, UV absorbers, pigments, dyes, lubricants, antiblocking agents, inorganic fillers, Examples include foaming agents. For example, organics such as azodicarbonamide, dinitrosopentamethylene diamine, sulfonyl hydrazide, sodium bicarbonate and ammonium bicarbonate in a ratio of about 0.1 to about 10 parts by weight per 100 parts by weight of the polymer components comprising the layer or Inorganic chemical blowing agents can be incorporated.

  The laminated film of the present invention can be produced by coextrusion as follows. The various component granules are melted in a suitable extruder and converted to film using conversion techniques. For coextrusion, the molten polymer is passed through a die or set of dies to form a layer of molten polymer that is processed as a laminar flow and then cooled to form a layered structure. The laminates of the present invention may also be produced by coextrusion followed by lamination onto one or more other layers. Suitable conversion techniques include blown film extrusion, cast film extrusion, cast sheet extrusion and extrusion coating.

  In addition to packaging materials, the laminates of the present invention include dicing tapes; semiconductor films such as adhesive tapes or back ground films; electrical and electronic materials such as marking films, integrated circuit carrier tapes and tapes for taping electronic components. Food packaging materials; medical supplies; protective films (eg, glass, plastic or metal plates and lenses, guard films or sheets); steel wire covering materials; clean room curtains; wallpaper; mats; floor finishes; Inner bag; Container; Shoes; Battery separator; Moisture permeable film; Antifouling film; Dustproof film; Film without PVC; Tubes for packs of cosmetics, detergents, shampoos, rinses, etc., base materials such as bottles Can be used.

  According to the present invention, a laminate that is excellent in charge attenuating property and can prevent dust and powder from adhering to it due to charging is excellent in antifouling property. Such laminates are used in the form of films, tapes, sheets, tubes, pipes, bags, multilayer containers (eg, containers made by blow molding), rods, various injection molded articles, various blow molded articles, and the like. be able to. Laminates in the form of films, sheets, bags or multilayer containers are preferred. In such a case, a molded article having a surface layer having an attenuation characteristic that forms the outer layer of the article has excellent antifouling properties, and surface contamination can be avoided. Furthermore, if the laminate is used as a powder packaging material and it is used in such a way that the surface layer with damping properties is the inner surface layer, no powder will be electrostatically applied to the packaging material. They do not stick and therefore their commercial value does not decrease.

  As indicated above, another aspect of the present invention is a multilayer blown container comprising a laminate of the present invention having as its intermediate layer a layer comprising the organic acid salt modified potassium ionomer composition of the present invention. The first and second surface layers are made of polyethylene such as low, medium or high density polyethylene or an ethylene-unsaturated ester copolymer such as ethylene-vinyl acetate copolymer, and the intermediate layer is the organic acid of the present invention. Of particular note is a laminated structure comprising a three-layer structure of a first surface layer (outer layer) / intermediate layer / second surface layer (inner layer) made of a salt-modified potassium ionomer composition. The multilayer blown container including the laminate of the present invention has an outer layer excellent in slipperiness, scratch resistance and antifouling property.

  Without further details, one of ordinary skill in the art using the preceding description will be able to make the most of the invention. Therefore, the following examples are merely illustrative and do not limit the present disclosure in any way. The raw materials used in the following Examples and Comparative Examples and the evaluation method of the antistatic performance of the obtained laminate are shown below.

(Materials used)
Ionomer 1 is ethylene, n-butyl acrylate (23.5 wt.%) And methacrylic acid (9 wt.%) Having a melt index of 1, neutralized 52% (nominally) with sodium hydroxide using sodium hydroxide. ).

  Ionomer 2 is a copolymer comprising ethylene and methacrylic acid (10 weight percent), having a melt index of 1.3, neutralized 55% (nominally) with sodium hydroxide using sodium hydroxide.

  Ionomer 3 is a copolymer comprising ethylene and methacrylic acid (19 weight percent) having a melt index of 2.6, neutralized with sodium hydroxide 37% (nominally) with sodium.

  PEG-1 is a polyethylene glycol having an average molecular weight of 100,000 gm / mole (available as Polyox WSRN-10 from Union Carbide).

(General procedure)
Using a Warner & Pfleiderer twin screw extruder, ionomer 1 was melt blended with potassium stearate at 15%, 30% and 40% by weight to provide Examples 1-3. did.

  Similarly, ionomer 2 was melt blended with potassium stearate at 15%, 30% and 40% by weight to provide Examples 4-6. Ionomer 3 was melt blended with potassium stearate at 40% by weight to provide Example 8.

  Examples 3A and 6A were based on the same composition as Examples 3 and 6, except that a longer barrel extruder with higher strength screws was used for melt blending.

  Examples 7, 9 and 10 are examples 3A and 6A with longer barrel extruders and higher strength screws, along with an additional stoichiometric amount of potassium hydroxide to neutralize the composition to 100% nominal neutralization. Manufactured in the same manner.

  Using the Warner and Pfriderer twin screw extruder with extended barrel length and higher strength screw, the indicated ionomer, potassium stearate and PEG-1 were mixed to 100% nominal neutralization of the composition. Examples 11-13 were prepared by melt blending with an additional stoichiometric amount of potassium hydroxide to sum.

  Chemistry to neutralize the indicated ionomer and isostearic acid to 100% nominal neutralization using an extended barrel length and a higher strength screw Warner and Pfriderer twin screw extruder. Examples 14-15 were prepared by melt blending with a stoichiometric amount of potassium hydroxide.

  Example 16 was prepared by melt blending Example 14 and Ionomer 3 in a 50:50 blend ratio on a Warner and Pfüderer twin screw extruder.

  The composition was then converted to a single layer blown film or cast film about 3 mils thick using a laboratory scale blown film apparatus or extrusion casting apparatus.

  Example compositions are summarized in Table 1. "..." means that the component is not present in the composition.

  The surface resistance of the film was measured as ohm / square and reported in Table 2. “NA” means that a measured value was not obtained.

  The surface resistance test was performed according to the American Society for Testing and Materials (ASTM) D-257 method.

なお、本発明の好ましい態様としては以下のものを挙げることができる。
１．（１）（ｉ）Ｅがエチレンであり、ＸがＣ_３〜Ｃ_８α，βエチレン性不飽和カルボン酸であり、そしてＹが、アルキル基が１〜８個の炭素原子を有するアクリル酸アルキルおよびメタクリル酸アルキルから選択された軟化コモノマーである少なくとも１つのＥ／Ｘ／Ｙ共重合体であって、ＸがＥ／Ｘ／Ｙ共重合体の約２〜３０重量％であり、かつ、ＹがＥ／Ｘ／Ｙ共重合体の約０〜４０重量％であるＥ／Ｘ／Ｙ共重合体と、
（ｉｉ）ブレンドの全成分中の組合せられた酸カルボン酸官能基が少なくとも部分的にカリウムによって中和されている、１つまたは複数の有機酸またはその塩と
のブレンドを含む少なくとも１つのポリマー層、および
（２）ポリマー材料を含む少なくとも１つの表層
を含むことを特徴とする多層積層物品。
２．（ｉｉ）が６〜３６個の炭素原子を有する脂肪族一官能基性有機酸、またはその塩から選択されることを特徴とする１に記載の物品。
３．（ｉｉ）がクエン酸またはその塩であることを特徴とする１に記載の物品。
４．（ｉ）がエチレン、２３．５重量％のアクリル酸ｎ−ブチルおよび９重量％のメタクリル酸を含む三元共重合体であり、かつ、（ｉｉ）がカリウムで名目上１００％中和された約３０〜約４０重量％のステアリン酸カリウムからであることを特徴とする１に記載の物品。
５．（ｉ）がエチレンおよび少なくとも１０重量％のメタクリル酸を含む共重合体であり、かつ、（ｉｉ）がカリウムで名目上１００％中和された約３０〜約４０重量％のステアリン酸カリウムからであることを特徴とする１に記載の物品。
６．２つのポリマー層より本質的になることを特徴とする１に記載の物品。
７．２つの表層と１つの中間層とがあり、かつ、（ｉ）が前記２つの表層間に配置された中間層であることを特徴とする少なくとも３つの層を含む１に記載の物品。
８．前記中間層が
（ａ）エチレン、２３．５重量％のアクリル酸ｎ−ブチルおよび９重量％のメタクリル酸を含む三元共重合体と、
（ｂ）カリウムで名目上１００％中和された４０重量％のステアリン酸カリウムと
のブレンドを含むことを特徴とする７に記載の物品。
９．前記中間層が
（ａ）エチレンおよび少なくとも１０重量パーセントのメタクリル酸を含む三元共重合体と、
（ｂ）約３０〜約４０重量％の名目上１００％中和されたステアリン酸カリウムと
のブレンドを含むことを特徴とする７に記載の物品。
１０．前記表層の少なくとも１つが亜鉛アイオノマーと、メタロセン触媒を用いて製造されたエチレンをベースとするポリマーとから選択されたポリマー材料よりなることを特徴とする７に記載の物品。
１１．前記表層の少なくとも１つと前記中間層との間に配置されている接着層または回収層から選択された少なくとも１つの追加層を含むことを特徴とする７に記載の物品。
１２．シート、バッグまたは多層容器の形状にあることを特徴とする７に記載の物品。
１３．包装に使用されるシートであることを特徴とする１２に記載の物品。
１４．ブロー成形によって得られることを特徴とする１３に記載の多層容器。
１５．テープ、シート、チューブ、パイプ、バッグ、ロッド；ダイシングテープ；接着テープまたは裏面研削フィルムのような半導体用フィルム；マーキングフィルム、集積回路キャリアテープおよび電子部品のテーピング用テープのような電気および電子材料；食品包装用材料；医療用品；保護フィルム（例えば、ガラス、プラスチックまたは金属の板およびレンズ、のガードフィルムまたはシート）；鋼線被覆材料；クリーンルームカーテン；壁紙；マット；床仕上げ材；フレキシブルコンテナの内部バッグ；容器；靴；電池セパレーター；透湿フィルム；防汚フィルム；防塵フィルム；ＰＶＣなしフィルム；チューブ、容器よりなる群の物品から選択された物品であることを特徴とする１に記載の物品。
１６．ブロー成形または射出成形によって得られることを特徴とする１に記載の物品。
２．（ｉ）Ｅがエチレンであり、ＸがＣ_３〜Ｃ_８α，βエチレン性不飽和カルボン酸であり、そしてＹが、アルキル基が１〜８個の炭素原子を有するアクリル酸アルキルおよびメタクリル酸アルキルから選択された軟化コモノマーである少なくとも１つのＥ／Ｘ／Ｙ共重合体であって、ＸがＥ／Ｘ／Ｙ共重合体の約２〜３０重量％であり、かつ、ＹがＥ／Ｘ／Ｙ共重合体の約０〜４０重量％であるＥ／Ｘ／Ｙ共重合体と、
（ｉｉ）ブレンドの全成分中の組合せられた酸カルボン酸官能基が少なくとも部分的にカリウムによって中和されている、１つまたは複数の有機酸またはその塩と
（ｉｉｉ）約９５重量％未満の量の熱可塑性ポリマーと
のブレンドを含むことを特徴とする帯電防止組成物。
１８．１７に記載の組成物を含むことを特徴とする物品。
１９．テープ、シート、チューブ、パイプ、バッグ、ロッド；ダイシングテープ；接着テープまたは裏面研削フィルムのような半導体用フィルム；マーキングフィルム、集積回路キャリアテープおよび電子部品のテーピング用テープのような電気および電子材料；食品包装用材料；医療用品；保護フィルム（例えば、ガラス、プラスチックまたは金属の板およびレンズ、のガードフィルムまたはシート）；鋼線被覆材料；クリーンルームカーテン；壁紙；マット；床仕上げ材；フレキシブルコンテナの内部バッグ；容器；靴；電池セパレーター；透湿フィルム；防汚フィルム；防塵フィルム；ＰＶＣなしフィルム；チューブ、容器よりなる群の物品から選択された物品であることを特徴とする１８に記載の物品。
２０．ブロー成形または射出成形によって得られることを特徴とする１８に記載の物品。

In addition, the following can be mentioned as a preferable aspect of this invention.
1. (1) (i) E is ethylene, X is _C 3 _{~C 8 α, β-ethylenically} unsaturated carboxylic acid, and Y is an alkyl acrylate wherein the alkyl group has from 1 to 8 carbon atoms And at least one E / X / Y copolymer that is a softening comonomer selected from alkyl methacrylate, wherein X is about 2-30% by weight of the E / X / Y copolymer, and Y An E / X / Y copolymer in which is about 0-40% by weight of the E / X / Y copolymer;
(Ii) at least one polymer layer comprising a blend with one or more organic acids or salts thereof wherein the combined acid carboxylic acid functionality in all components of the blend is at least partially neutralized by potassium. And (2) a multilayer laminate article comprising at least one surface layer comprising a polymeric material.
2. 2. The article according to 1, wherein (ii) is selected from aliphatic monofunctional organic acids having 6 to 36 carbon atoms, or salts thereof.
3. 2. The article according to 1, wherein (ii) is citric acid or a salt thereof.
4). (I) is a terpolymer comprising ethylene, 23.5 wt% n-butyl acrylate and 9 wt% methacrylic acid, and (ii) is nominally 100% neutralized with potassium The article of 1, wherein the article is from about 30 to about 40 weight percent potassium stearate.
5). (I) is a copolymer comprising ethylene and at least 10% by weight methacrylic acid, and (ii) from about 30 to about 40% by weight potassium stearate nominally 100% neutralized with potassium. 2. The article according to 1, wherein the article is present.
6. The article of 1, characterized in that it consists essentially of two polymer layers.
7. The article according to 1, comprising at least three layers, wherein there are two surface layers and one intermediate layer, and (i) is an intermediate layer disposed between the two surface layers.
8). A terpolymer wherein the intermediate layer comprises (a) ethylene, 23.5 wt% n-butyl acrylate and 9 wt% methacrylic acid;
(B) Article according to 7, characterized in that it comprises a blend with 40% by weight potassium stearate nominally 100% neutralized with potassium.
9. The intermediate layer comprises (a) a terpolymer comprising ethylene and at least 10 weight percent methacrylic acid;
(B) The article of claim 7, comprising a blend with about 30 to about 40% by weight of nominally 100% neutralized potassium stearate.
10. Article according to claim 7, characterized in that at least one of the surface layers consists of a polymer material selected from a zinc ionomer and an ethylene-based polymer produced using a metallocene catalyst.
11. The article according to claim 7, comprising at least one additional layer selected from an adhesive layer or a recovery layer disposed between at least one of the surface layers and the intermediate layer.
12 8. Article according to 7, characterized in that it is in the form of a sheet, bag or multilayer container.
13. 13. The article according to 12, which is a sheet used for packaging.
14 14. The multilayer container according to 13, which is obtained by blow molding.
15. Tapes, sheets, tubes, pipes, bags, rods; dicing tapes; semiconductor films such as adhesive tapes or back ground films; electrical and electronic materials such as marking films, integrated circuit carrier tapes and tapes for taping electronic components; Food packaging materials; medical supplies; protective films (eg glass, plastic or metal plates and lenses, guard films or sheets); steel wire covering materials; clean room curtains; wallpaper; mats; floor finishes; 1. The article according to 1, which is an article selected from the group consisting of a bag, a container, shoes, a battery separator, a moisture permeable film, an antifouling film, a dustproof film, a PVC-free film, a tube and a container.
16. 2. The article according to 1, which is obtained by blow molding or injection molding.
2. (I) E is ethylene, X is C ₃ ~C ₈ α, β-ethylenically unsaturated carboxylic acid, and Y is acrylic acid alkyl and alkyl methacrylate group having 1 to 8 carbon atoms At least one E / X / Y copolymer that is a softening comonomer selected from alkyl, wherein X is about 2-30 wt% of the E / X / Y copolymer, and Y is E / An E / X / Y copolymer that is about 0-40% by weight of the X / Y copolymer;
(Ii) one or more organic acids or salts thereof in which the combined acid carboxylic acid functionality in all components of the blend is at least partially neutralized by potassium; (iii) less than about 95% by weight An antistatic composition comprising a blend with an amount of a thermoplastic polymer.
18. An article comprising the composition according to 18.17.
19. Tapes, sheets, tubes, pipes, bags, rods; dicing tapes; semiconductor films such as adhesive tapes or back ground films; electrical and electronic materials such as marking films, integrated circuit carrier tapes and tapes for taping electronic components; Food packaging materials; medical supplies; protective films (eg glass, plastic or metal plates and lenses, guard films or sheets); steel wire covering materials; clean room curtains; wallpaper; mats; floor finishes; 19. The article according to 18, which is an article selected from the group consisting of a bag, a container, shoes, a battery separator, a moisture permeable film, an antifouling film, a dustproof film, a PVC-free film, a tube and a container.
20. 19. The article according to 18, which is obtained by blow molding or injection molding.

Claims (2)

(1) (i) E is ethylene, X is _C 3 _{~C 8 α, β-ethylenically} unsaturated carboxylic acid, and Y is an alkyl acrylate wherein the alkyl group has from 1 to 8 carbon atoms And an ionomer of at least one E / X / Y copolymer that is a softening comonomer selected from alkyl methacrylate, wherein X is 2-30% by weight of the ionomer of the E / X / Y copolymer; and, an ionomer of E / X / Y copolymer and Y is 0-40 weight% of an ionomer of E / X / Y copolymer,
(Ii) blends with one or more organic acids and salts thereof, or salts of one or more organic acids ,
Wherein at least one polymer layer comprising a blend wherein the combined carboxylic acid functional groups in all components of the blend are at least partially neutralized by potassium , and (2) comprising at least a polymer material A multilayer laminated film comprising one surface layer. (I) E is ethylene, X is C ₃ ~C ₈ α, β-ethylenically unsaturated carboxylic acid, and Y is acrylic acid alkyl and alkyl methacrylate group having 1 to 8 carbon atoms An ionomer of at least one E / X / Y copolymer that is a softening comonomer selected from alkyl, wherein X is 2-30% by weight of the ionomer of the E / X / Y copolymer, and Y There an ionomer of E / X / Y copolymer is 0-40 weight percent of an ionomer of E / X / Y copolymer,
(Ii) one or more organic acids and salts thereof, or one or more salts of organic acids
A blend of
Wherein the combined carboxylic acid functional groups in all components of the blend are at least partially neutralized with potassium, and (iii) comprise an amount of thermoplastic polymer in an amount of less than 95% by weight. An antistatic composition for film formation .